Carboxylic acid esters derived from 1,2-bis-(3-cyclohexen-1-yl)-ethylene and derivatives thereof



United States Patent 3,433,828 CARBOXYLIC ACID ESTERS DERIVED FROM 1,2-BIS-(3-CYCLOHEXEN-1-YL)-ETHYLENE AND DE- RIVATIVES THEREOF John R.Norell, Bartlesville, Okla., assignor to Phillips Petroleum Company, acorporation of Delaware No Drawing. Filed Oct. 22, 1965, Ser. No.502,332 US. Cl. 260-487 7 Claims Int. Cl. C07c 69/62, 69/7 6, 69/22ABSTRACT OF THE DISCLOSURE Novel esters and alcohols are formed from1,2-bis(3- cyclohexen-l-yl)-ethylene and derivatives thereof.

This invention relates to a process for the esterification of noveltriolefins and also to the esters formed in said process. In anotheraspect this invention relates to the formation of alcohols by thesaponification of said novel esters. In another aspect this inventionrelates to the hydrogenation of those alcohols possessing olefinicunsaturation. In another aspect this invention relates to a process forthe esterification of 1,2 bis(3 cyclohexen-l-yl)- ethylene.

According to the invention, novel compounds are prepared by esterifyingtriolefins characterized by the following formula:

RR RR R I I l R RR RR RR RR where R is at least one member selected fromthe group consisting of hydrogen, methyl and ethyl, the total number ofcarbon atoms in all of said Rs preferably being not greater than 8.

The preparation of these triolefins is described in a copendingapplication of D. L. Crain, Ser. No. 502,544, filed Oct. 22, 1965assigned to a common assignee, Phillips Petroleum Company ofBartlesville, Oklahoma.

It is also within the scope of the present invention that these novelesters can then be saponified to form the mono-ols, diols, and/ortriols. Furthermore, it is within the scope of this invention that themono-01s and/ or diols can be hydrogenated to form saturated mono-01sand/or diols.

Specific examples of those materials which can be used as the startingmaterial in the esterification are as follows:

1,2-bis 3-cyclohexenl-yl ethylene 1,2-bis( l-rnethyl-3 -cyclohexenl-yl)ethylene 1,2-bis 2-methyl-3 -cyclohexenl-yl) ethylene 1,2-bis (3-ethyl-3-cyclohexen-1-yl )ethylene l,2-bis (4-methyl-3 -cyclohexen-1-yl)ethylene 1,2-bis 5-ethyl-3 -cyclohexenl-yl) ethylene 1,2-bis(6,6-dirnethyl-3 -cyclohexenl-yl) ethylene 3,4-bis (3-cyclohexen-l-yl -3hexene 1,2-bis (2,6-dimethyl-3-cyclohexenl-yl) ethylene 2,3 -bis (3-methyl-3 -cyclohexen-1-yl) -2-butene 1,2-bis 1,3 -dimethyl-3-cyclohexen-1-yl)ethylene 2,3-bis (4-methyl-3-cyclohexenl-yl -2-butene1,2-bis( 1,4-dimethyl-3-cyclohexen-l-yl ethylene 1,2-bis 5 ,6-dimethyl-3-cyclohexenl-yl) ethylene 2,3 -bis 1,3 ,4-trimethyl-3-cycl ohexenl-yl)-2-butene 1,2-bis 2,5 ,6 -trimethyl-3 -cyclohexen-1-yl ethylenel,2-bis(2,6-diethyl-3-cyclohexen-l-yl ethylene 3 ,4-bis (4-ethyl-3-cyclohexen-1-yl) -3 -hexene 1-(3 methyl 3 cyclohexenl-yl)-2-(2-methyl-6-ethyl- 3 -cyclohexenl-yl) -ethylene 3,433,828Patented Mar. 18, 1969 l (3 cyclohexen l yl)-2-(2 methyl-3-cyclohexen-1-yl)ethylene.

wherein R is selected from the group consisting of hydrogen and alkyl,aryl, and cycloalkyl radicals and combinations thereof such as alkaryland aralkyl radicals, and alpha-haloalkyl radicals, each of saidradicals containing from 1 to 10 carbon atoms inclusive.

Specific examples of acids which can be employed are formic acid, aceticacid, propionic acid, isobutyric acid, n-octanoic acid, n-decanoic acid,n-undecanoic acid, benzoic acid, 4 n-butylbenzoic acid,cyclohexanecarboxylic acid, S-phenylvaleric acid, chloroacetic acid,trichloroacetic acid, dibromoacetic acid, trifluoroacetic acid, and thelike.

Catalysts that can be used for this process are the acid-type, forexample, sulfuric acid, boron trifluoride, boron trifluoride-ethercomplex, stannic chloride and ferric chloride.

Diluents that can be employed if desired include chloroform, carbontetrachloride, and 1,1,2-trichloroethane. The choice of diluent willdepend upon the particular organic acid chosen, but whatever diluent isused, both the triene reactant and the organic acid reactant should besoluble in the diluent. The amount of diluent employed can vary over awide range, but will generally range from l00-1,500 ml. per mol oftriene being reacted. If desired, the acid reactant can serve as adiluent.

In forming the mono-, di-, and/or triesters, the reaction temperaturewill generally range from 20-120 C. with the preferred range being fromabout 50-70 0., when a catalyst is employed. In those situations whereinthe reaction is carried out in the absence of a catalyst, the preferredtemperature range is from about 70-l00 C. The amount of catalystemployed can vary widely,

but will generally range from about 1l0 weight percent based on the1,2-bis(3-cyclobexen-l-yl)ethylene. The reaction time for formation ofthe mono-, di-, and/or triesters can range from a few minutes up toseveral days, but generally will range from about 10-30 hours.

Although the monoesters predominate at low acidztrieue mol ratios suchas 1:1 or less, higher acid:triene mol ratios such as 2:1 give diestersas the principal products; substantial amounts of the triesters areproduced with further increase of the acidztriene ratio. Less reactiveacids often yield the monoesters as the major product even though anexcess of acid is used. As the cycloolefinic double bonds tend to bemore reactive than the ethylenic double bond in this process, the majoramount of the monoesters and diesters will generally be those in whichthe ethylenic double bond remains intact. saponification of these estersby the process of this invention results in the formation of thecorresponding mono-01s, diols, and triols. In the process of thisinvention, formic acid is the preferred reacting acid if one is toprepare alcohols in a subsequent saponification step. If the estersthemselves are the desired products, the chosen acid will depend uponthe desired properties such as boiling point, etc., of the esters.

Examples of esters produced according to the abovedescribed processconsist of compounds characterized by the following formulas:

Monoesters having the formulas R R R and and

R XII X XII R R R R R R R R where R is at least one member selected fromthe group consisting of hydrogen, methyl and ethyl, the total number ofcarbon atoms in all of said Rs being not greater than 8; and each X, Xand X" is a member selected from the group consisting of and hydrogen,one and only one X, one and only one X, and one and only one X beingwhere R' is a member selected from the group consisting of hydrogen andalkyl, aryl, and cycloalkyl, alkaryl, aralkyl, and alphahaloalkylradicals, each of said radicals containing not more than 10 carbonatoms.

It is to be understood that the esters which are produced by the processof this invention are formed as mixtures from which the pure compoundscan be recovered by suitable means. For example, the reaction ofbis(3-cyclohexen-1-yl)ethylene and derivatives with formic acid andother acids according to the process of this invention gives thefollowing compounds:

1- (3 -formyloxycyclohexyl) -2- (4-formyloxycyclohexyl) ethylene1-formyloxy-1,2-bis(3-formyloxycyclohexyl) ethane 1-formyloxy-1,2-bis(4-for-myloxycyclohexyl) ethane l-forrnyloxy- 1- 3 -formyloxycyclohexyl)-2- (4-formyloxycyclohexyl) ethane l -formy1oxy- 14-formyloxycyclohexyl) -2/- 3 -f0rmyltoxycyclohexyl) ethane l-acetoxy-l,2-bis 3-cyclohexen l-yl) ethane 1- (3-cyclohexen- 1-y1) -2-3-acetoxycyclohexyl) ethylene 1- 3 -cyclohexenl -yl -2-(4-acetoxycyclohexyl ethylene 1,2-bis 3 -acetoxycyclohexyl) ethylene1,2-bis (4-acetoxycycl0hexyl) ethylene 1- 3 -acetoxycyclohexyl -2-(4-acetoxycyclohexyl) ethylene l-acetoxy-1,2-bis(3-acetoxycyclohexyl)ethane l- (chloro acetoxy) -1 ,2-bis 3-cyclohexen-l -yl) ethane l- (3-cyclohexenl -yl) -2- 3- (chloroacetoxy) cyclohexyl] ethylene l-3-cyclohexenl-yl) -2- [4-chloroac etoxy) cyclohexyl] ethylene 1,2-bis[3- chloro acetoxy) cyclohexyl] ethylene l,2-bis [4- (chloroacetoxy)cyclohexyl] ethylene 1- 3- chloroacetoxy) cyclohexyl] -2- [4- (chloroacetoxy) cyclohexyl] ethylene 1- 3-cyclohexenl-yl) -2- 3-dibromoacetoxy)cyclohexyl] ethylene 1-(3-cyclohexen-l-yl) -2-[4-(trifluoroacetoxy)cyclohexyl] ethylene 1- 6-methyl-3-cyclohexen- 1-yl) -2- 3 -butyloxycyclohexyl) ethylene 1,2-bis (3-ethyl-5-hexanoyloxycyclohexyl) ethylene 2- (3 -methyl-3-cyclohexenl-yl) -3 3 -methyl-4-undecanoyloxycyclohexyl) RZ-butene 3-(2,2-dimethyl-3-cyclohexen-l-yl -4- (2,2-dimethyl-3- benzoyloxycyclohexyl) -3-hexene ll-methyl-4-ethyl-3 -cyclohexen-1-yl) -2-l-ethyl-3- methyl-4- cyclopentanoyloxycyclohexyl ethylene 1-(3-cyclohexen-1-yl) -2- (3-p-toluoyloxycyclohexyl) ethylene 1- 3-cyclohexen-1-yl -2- [4 phenylacetoxy) cyclohexyl] ethylene As describedhereinabove, it is also within the scope of this invention to convertthese esters to alcohols, including the mono-01s, diols, triols, andmixtures thereof by saponification with a base. Suitable bases includesodium hydroxide and potassium hydroxide. The amount of base presentshould be at least one equivalent per ester group present in the esterbeing saponified and can range as high as 3-5 equivalents per estergroup present. This saponification is preferably carried out in anaqueous system using from about SOD-4,500 ml. of water per mol of esterbeing saponified. The saponification is carried out at a temperaturegenerally ranging from 50l20 C. and a period of time generally rangingfrom a few minutes to several days, and more usually less than 24 hours.

Following saponification, the produced alcohols can be recovered fromthe reaction mixture by such methods as fractional crystallization,distillation, solvent extraction, and the like.

The alcohols produced by the saponification of the esters can becharacterized by the following formulas:

Mono-01s having the formulas R RR RR R R R R R Y Y R RR RR RR RR and RRRRR RY RR \l I/ Y R- RR R RR RR RR RR and diols having the formulas R R R-R R R Y R R I T E R Y Y R R RR RR RR RR and Y R R R R R R Y Y \I I R RI I R l R R R R R R R R R R R and triols having the formula Y R R R R RR Y" 1 1/ 2 f: \l

R R Y! R R R R R R R R R R where R is at least one member selected fromthe group consisting of hydrogen, and methyl and ethyl, the total numberof carbon atoms in all of said R groups preferably being not greaterthan 8; and each Y, Y and Y" is a member selected from the groupconsisting of hydroxyl and hydrogen, one and only one Y, one and onlyone Y, and one and only one Y" being hydroxyl.

Specific examples of these compounds are as follows:

l-hydroxy-l ,2-bis( 3-cyclohexen-1-y1) ethane 1- 3-cyclohexen-1-yl -2-(3 -hydroxycyclohexyl) ethylene 1- (3 -cyclohexen-1-yl) -2-4-hydroxycyclohexyl) ethylene 1-hydr0xy-1-( 3 -cyclohexen-1-yl) -2-(3-hydroxycyclohexyl) ethane 1-hydroxy-1-( 3 -cyclohexen-1-yl) -2-(4-hydroxycyclohex'yl) ethane 1-hydroxy-1-(3 -hydroxyoydlohexyl) -2- (3-cyclohexenl-yl ethane l-hydroxy- 1 (4-hydroxycyclohexyl) -2- (=3-cyclohexenl-yl ethane 1 ,2-bis 3 -hydroxycyclohexyl) ethylene 1,2-Jbis4-hydroxycyclohexyl ethylene 1-( 3 -hydroxycyclohexyl) -2-(4-hydroxycyclohexyl) ethylene 1-hydroxy-l,2-bis( 3 -hydroxycyclohexyl)ethane l-hydroxy-l ,2-bis (4-hydroxycyclohexyl) ethane 1-hydroxy-1-( 3-hydroxycyclohexyl) -2- 4-hydroxycyclohexyl) ethane1-hydroxy-1-(4-hydroxycyc1ohexyl) -2- (3 -hydroxycyclohexyl ethane 1-(6-methyl-3 -cyclohexen-1yl) -2- 3 -hydroxycyclohexyl) ethylene 1,2-bis(3 -ethyl--hydroxycyclohexyl) ethylene 2-( 3 -methyl-3 -cyclohexenl-yl)-3 (.3 -methyl-4- hydroxycyclohexyl -2-butene 3-2,2-dimethyl-3-cyclohexen-1-yl) -4- (2,2-dinnethyl- 3 -hydroxycyclohexyl-3 -hexene 1-( 1-methyl-4-ethyl-3 -cyclohexen-1-yl) -2-( l-ethyl- 3-methyl-4-hydroxycyclohexyl ethylene It is further within the scope ofthis invention that those alcohols possessing olefinic nnsaturation canbe hydrogenated by passing them over a catalyst which is selected fromthe group consisting of platinum, palladium, Raney nickel, or the like.This hydrogenation can be carried out in any of the conventionalsolvents such as ethanol, dioxane, tetrahydrofuran, or the like. Thehydrogenation temperature can vary over a wide range; however, it willusually be within the range of about room temperature to about 100 C.The hydrogenation pressure can be as high as 2,000 p.s.i.g. or higher;however, it is usually maintained within the range of about atmosphericpressure to about 200 p.s.i.g.

The esters prepared by the process of this invention are useful asplasticizers. The alcohols prepared by the saponification of theseesters are useful as intermediates in the formation of polyesters andpolyurethanes. The

ethylenic double bond which is available in some of these A run wascarried out in which 1,2-bis(3-cyclohexen-1- yl)ethylene was reactedwith formic acid to produce formate esters according to the process ofthis invention.

Formic acid (98-100 percent) g., 1.74 mol) and1,2-bis(3-cyclohexen-1-yl)ethylene (33.2 g., 0.18 mol) were placed in a200 ml. 3-necked flask and heated at 100 0. without a solvent orcatalyst for 5 hours, with stirring. The mixture was allowed to standovernight and was then diluted with water and extracted with ether. Theether layer was washed with saturated sodium bicarbonate solution andthen with water. The ether solution was dried over magnesium sulfate,and the solvent was removed, leaving as a residue 37.1 -g. of a liquidwhich was distilled to give 5 fractions. Fraction 1 (11.6 g., B.P. 79-110 C./ 0.4 mm., 11 1.5087) was principally unreacted1,2-bis(3-cyclohexen-l-yl)ethylene. Fractions 2, 3 and 4 (11.8 g., B.P.112-150 C./0.5-0.4 mm., n 1.4996-1.4972) were primarily a mixture of1-(3-cyclohexen-1-yl)-2-(3-formyloxycyclohexyl)ethylene and 1-(3-cyclohexen 1 yl) 2 (4 formyloxycyclohexyl)ethylene. Fraction 5 (8.0 g.,B.P. 15'0-142 'C./0.40.2 mm., n 1.4920) was primarily a mixture of1,2-bis(3-formyloxycyclohexyl)ethylene, 1,2-bis(4-formyloxycyclohexyl)ethylene, and1-(3-formyloxycyclohexyl)-2-(4-formyloxycyclohexyl)ethylene. Nuclearmagnetic resonance analysis of fraction 5 showed the ratio of formatehydrogens to olefinic hydrogens to be about 1311, indicating thepresence of about 20 mol percent triformate. About percent of theolefinic protons were of the ethylenic type, the remainder being of thecycloolefinic type.

EXAMPLE II 1,2-bis(3-cyclohexen-1-yl)ethylene (18.8 g., 0.10 mol) wasadded slowly to a stirred solution of chloroform (75 ml.), 98-100percent formic acid (50 g., 1.1 mol) and 10 drops of the concentrated HSO contained in a fully-equipped 200 ml. 3-necked tflask at 60 C. Themixture assumed a deep violet coloration and was heated overnight atCHCl reflux. The mixture was cooled and poured into an ice-NaHCO'mixture, and when neutralized, it was extracted with CHCl The organicextracts were dried over MgSO the solvent removed and the residuedistilled to give 9.1 g. (51.5 percent conversion) of starting1,2-bis(3-cyclohexen-1-yl)ethylene and 8.8 g. of formate esters of the1,2-bis(3-cyclohexen-l-yl) ethylene.

EXAMPLE HI A nun was carried out in which 1,2-bis(3-cyclohexen-1-yl)ethylene was reacted with formic acid, in the presence of a catalyst,to form diesters according to the process of this invention.

In this run, a 2,000 ml., 4-necked flask fitted with a stirrer,condenser, addition funnel and thermometer was charged with 550 ml. ofchloroform, 550 grams of 98- 100 percent formic acid and 35 ml. of BF-(C H O in that order. The contents of the flask were heated to 60-65 C.while stirring and 250 grams of 1,2-bis(3-cyclohexen-l-yl)ethylene wasadded to the mixture over a 1.5-2 hour period. The resultingviolet-colored solution was stirred and maintained at reflux temperature(65 C.) for 12-15 hours.

Because of the volume of the solution, the product was worked up in twoportions. After the material had been cooled to room temperature, halfof the mixture was poured onto a slurry of ice and sat-urated sodiumbicarbonate solution. The slurry contained approximately 200 grams ofice and 250 ml. sodium bicarbonate solution. The ice slurry was stirredvigorously while adding the reaction mixture to the slurry. The otherhalf of the reaction mixture was treated in the same manner. The organiclayer which separated was recovered and the aqueous layer in eachtreatment was extracted once with approximately 200 ml. of chloroform.This extract was added to the organic layer, after which the organiclayer was again contacted with approximately 300 ml. of saturated sodiumbicarbonate solution. After drying, the organic layer was charged to arotary evaporator, and the chloroform was stripped off.

After removing the chloroform, the remaining material was distilledthrough a 12-inch Vigreaux column and 166 grams of diesters, boilingrange 1401'58 C. at 0.2 mm. mercury absolute pressure, was obtained.Further distillation of this material yielded a close-boiling fraction,boiling point 155-157 C. at 0.2 mm. mercury absolute pressure. Therefractive index (n of this fraction was 1.4972. This fraction wasprimarily a mixture of the diesters1,2-bis(3-formyloxycyclohexyl)ethylene,1,2-bis(4-formyloxycyclohexyl)ethylene, and 1-(3-formyloxycyclohexyl) 2(4 formyloxycyclohexyl)ethylene. An elemental analysis of this materialgave the following results.

Elemental analysis (in wt. percent).-Calculated for C H O C, 68.5; H,8.6; O, 22.9. Found: C, 68.7; H, 8.6; O, 22.7 (by ditference).

EXAMPLE IV The diesters of Example III were saponified to form thecorresponding diols in the following manner.

A mixture of 230 grams of the diesters from Example III with a solutionof 120 grams of NaOH in 500 ml. of water was charged to a 1,000 ml.,3-necked flask fitted with a stirrer, condenser and thermometer. Themixture was heated to 90-100 C. and maintained at this temperature whilestirring for 12-15 hours. The heat source was then removed and stirringwas continued until the mixture had cooled to 25 C. The stirrer was thenremoved, and the aqueous layer was carefully decanted from the veryviscous organic layer. Approximately 500 ml. of water and approximately25 ml. of concentrated HCl were added to the flask and the mixture wasstirred. The ester layer was separated, and an additional 500 ml., ofwater was added, mixed and removed. Approximately 300 ml. of ethylacetate was added to the flask, and the mixture was heated on a steambath until all of the organic layer from the reaction was dissolved. Theresulting hot solution was filtered and then cooled in a refrigeratorovernight. Ninety-two grams of material, melting point 8795 C., clear at125 C., was obtained. When recrystallized from ethyl acetate a materialmelting at 119- 124 C. was obtained. This material was primarily amixture of the diols 1,2-bis(3-hydroxycyclohexyl)ethylene,1,2-bis(4-hydroxycyclohexyl)ethylene, and 1-(3-hydroxycyclohexyl)-2-(4hydroxycyclohexyl)ethylene. An elemental analysis of this material gavethe following results.

Elemental analysis (in wt. percent).Calculated for C I-1 C, 75.0; H,10.7; 0, 14.3. Found: C, 74.7; H, 10.7; 0, 14.6 (by difference).

EXAMPLE V A run was carried out in whichl,2-bis(3-cyclohexenl-yl)ethylene was reacted with acetice acid to formmonoesters.

In this run, 20 grams (0.30 mol) of acetic acid and grams of BF -(C H Owere dissolved in 70 m1. of chloroform and heated to 60 C. At this time,18.8 grams (0.1 mol) of 1,2-bis(3-cyclohexen-1-yl)ethylene was dissolvedin ml. of chloroform and added to the catalyst solution over a one hourperiod. The resulting mixture was heated to refiux (68 C.) for 6 hours,after which it was allowed to stand overnight and cool to roomtemperature. The solution was then poured into ice cold sodiumbicarbonate solution as in the previous examples. The organic layer wasseparated, washed with water and dried, after which the chloroform wasdistilled. The remaining dark residue was distilled at 0.2 mm. mercuryabsolute pressure, yielding five fractions which boiled at 70-71, 71-97,113-121, 121-130, and -167, all temperatures being given in degrees C.The last three fractions were combined and redistilled, and a fractionwas taken which boiled at 125-130 C. at 0.2 mm. mercury absolutepressure. The refractive index (12 of this material was 1.4934. Thefollowing elemental analysis of the product clearly shows this materialwas a monoester fraction, which consisted primarily of a mixture of1-(3- cyclohexen-l-yl) 2 (3-acetoxycyclohexyl)ethylene and 1-3-cyclohexen-1-yl) -2-(4-acetoxycyclohexyl) ethylene.

Elemental analysis (in wt. percent).Calculated for C H O C, 77.5; H,9.7; O, 12.8. Found: C, 76.8; H, 9.8; O, 13.4 (by difference). Thecalculated molecular weight for these monoesters is 248, and themeasured molecular weight of the material which was subjected toelemental analysis was 245. The infrared spectrum showed a carbonyl bandat 5.8 microns and a weak cyclohexyl band at 6.1 microns. The nuclearmagnetic resonance spectrum showed evidence for an equal amount ofcyclic nonterminal olefinic protons at 4.4T units and acyclicnonterminal olefinic protons at 4.67- units, indicating that the acetoxygroup was primarily on a cyclohexyl ring and not on the ethyleniclinkage.

EXAMPLE VI A run was carried out in which 1,2-bis(3-cyclohexen-1-yl)ethylene was converted to the monoesters by reaction withchloroacetic acid.

In this run, 18.8 grams (0.1 mol) of 1,2-bis(3-cyclohexen-1-yl)ethylenewas dissolved in 75 ml. of chloroform, and the resulting solution washeated to 35-40 C., after which 2.13 grams of BF -(C H O was added tothis solution. A solution of 18.9 grams (0.20 mol) of chloroacetic aciddissolved in 35 ml. of chloroform was then added dropwise over a 20minute period. The resulting solution was stirred at 40 C. for 6.5hours, after which the reaction mixture was poured into ice cold sodiumbicarbonate solution. The layers separated, and the organic layer wasremoved, washed with 150 ml. of sodium bicarbonate solution and dried.After the chloroform was removed, the 23.5 grams of residue remainingwas distilled. A fraction was obtained which boiled at 140 C. at 0.2 mm.mercury absolute pressure. The refractive index (11 of this material was1.5075. The following elemental analysis of this material clearly showsthat the product was a monoester fraction, which consisted primarily ofa mixture of 1-(3-cyclohexen-1-yl)-2-[3-(chloroacetoxy)cyclohexyl]ethylene and 1-3 cyclohexen- 1 -yl -2-[4- chloroacetoxy cyclohexyl] ethylene.

Elemental analysis (in wt. percent).-Calculated for C H ClO C, 68.0; H,8.2; Cl, 12.5; 0, 11.3. Found: C, 68.7; H, 8.2; Cl, 12.6; 0, 10.5 (bydifference).

EXAMPLE VII The mixture of unsaturated diols from Example IV wereconverted to the saturated diols in the following manner. Eleven andtwo-tenths grams (0.05 mol) of the unsaturated diols was dissolved inm1. of absolute ethanol and to this solution was added 0.1 gram ofreduced platinum oxide catalyst. This solution was then subjected tohydrogenation in a Parr apparatus. After 79 hours at 25 C. and 50p.s.i.g. initial hydrogen pressure, the pressure in the apparatus hadfallen to 24 p.s.i.g. This was approximately equivalent to a hydrogenuptake of 0.05 mol. The solution was filtered to remove the catalyst,after which the ethanol was distilled. A waxy solid was obtained whichwas recrystallized from a mixture of n-hexane and ethyl acetate to givea white powdery material melting over the range 96-105 C. Elementalanalysis confirmed this material to be a saturated diol product, whichconsisted primarily of a mixture of 1,2- bis(3-hydroxycyclohexyl)ethane,1,2-bis(4-hydroxycyclohexyl)ethane, and 1 (3hydroxycyclohexyl)-2-(4-hydroxycyclohexyl) ethane.

Elemental analysis (in wt. percent).-Calculated for C H O C, 74.3; H,11.6; 0, 14.2; molecular weight, 226. Found: C, 74.5; H, 11.5; 0, 15.4,molecular weight, 230.

Obviously, many modifications and variations of the present inventionare possible in the light of the above teachings. It is, therefore, tobe understood that within the scope of the appending claims theinvention may be practiced otherwise than is specifically describedherein.

Iclaim:

1. Novel ester compounds characterized by the following formulas:

monoesters having the formulas and and

and triesters having the formula wherein R' is a member selected fromthe group consisting of (1) hydrogen, (2) hydrocarbon radicals selectedfrom the group consisting of alkyl, aryl, cycloalkyl, alkaryl, andaralkyl, and (3) alpha-haloalkyl, each of said radicals containing notmore than carbon atoms.

10 2. Novel ester compounds characterized by the following formulas:

monoesters having the formulas and and

R R R R and triesters having the formula where R is hydrogen and each X,X and X" is a member selected from the group consisting of and hydrogen,one and only one X, one and only one X', and one and only one X" beingwhere R is a member selected from the group consisting of hydrogen,alkyl, and alpha-haloalkyl, each of said radicals containing not morethan 10 carbon atoms.

3. 1 (3 cyclohexen-l-yl)-2-(3-formyloxycyclohexyl) ethylene.

4. 1 (3-cyclohexen-1-yl)-2-(4-acetoxycyclohexyl)ethylene.

5. 1,2-bis [4- (chloroacetoxy) cyclohexyl] ethylene.

6. l-acetoxy-1,2-bis(3-acetoxycyclohexyl)ethane.

LORRAINE A. WEINBERGER, Primary Examiner. VIVIAN GARNER, AssistantExaminer.

US. Cl. X.R.

